A chelate like no other: exploring the synthesis, coordination chemistry and applications of imidoyl amidine frameworks

Kitos, Alexandros A.; Mavragani, Niki; Murugesu, Muralee; Brusso, Jaclyn L.

doi:10.1039/d0ma00720j

Cited by 5 publications

(8 citation statements)

References 116 publications

(72 reference statements)

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“…The addition of L1 – L4 apparently occurred via the nucleophilic attack of OMe – on the metal-activated nitrile group, whereupon an amino-group of L1 – L4 replaces the OMe moiety in the formed imino ester; the process is similar to the Pinner synthesis (for a review, see ref ). In addition, the base provides the deprotonation of the central imidoylamidinate N atom in the formed complexes. Alternatively, the methoxide group could activate the NH 2 functionality by deprotonation before the nucleophilic attack at the nitrile C center.…”

Section: Resultsmentioning

confidence: 99%

“…The coordination chemistry of imidoylamidinate (or triazapentadiene in another terminology 25 ) ligand has been reviewed. 26 The plan of this study was as follows. First, we prepared four iridium(III) complexes bearing both imidoylamidinate ligands and the cyclometalated 2-phenylbenzothiazole.…”

Section: Introductionmentioning

confidence: 99%

“…Notably, boron and platinum imidoylamidinate species exhibit useful luminescence properties and this indirectly stimulated our interest in studies of relevant iridium(III)-based systems. The coordination chemistry of imidoylamidinate (or triazapentadiene in another terminology) ligand has been reviewed …”

Section: Introductionmentioning

confidence: 99%

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Photo- and Electroluminescent Neutral Iridium(III) Complexes Bearing Imidoylamidinate Ligands

et al. 2022

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Imidoylamidinate-based heteroleptic bis(2phenylbenzothiazole)iridium(III) and -rhodium(III) complexes [(bt) Ir4); yields 70−84%) were obtained by the reaction of the in situ-generated solvento-complex [(bt) 2 M-(NCMe) 2 ]NO 3 and benzo[d]thia/oxa/N-methylimidozol-2amines in the presence of NaOMe. Complexes Ir1−4 exhibited intense orange photoluminescence, reaching 37% at room temperature quantum yields, being immobilized in a poly(methyl methacrylate) matrix. A photophysical study of these species in a CH 2 Cl 2 solution, neat powder, and frozen (77 K) MeOC 2 H 4 OH− EtOH glass matrixalong with density-functional theory (DFT), ab initio methods, and spin−orbit coupling time-dependent DFT calculationsverified the effects of substitution in the imidoylamidinate ligands on the excited-state properties. Electrochemical (cyclic voltammetry and differential pulse voltammetry) and theoretical DFT studies demonstrated noninnocent behavior of the imidoylamidinate ligands in Ir1−4 and Rh1 complexes due to the significant contribution coming from these ligands in the HOMO of the complexes. The iridium(III) species exhibit a ligand (L, 2-phenylbenzothiazole)-centered ( 3 LC), metal-to-ligand (L′, imidoylamidinate) charge-transfer ( 3 ML′CT, 3 MLCT) character of their emission. The imidoylamidinate-based iridium(III) species were proved to be effective as the emissive dopant in an organic light-emitting diode device, fabricated in the framework of this study.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Photo- and Electroluminescent Neutral Iridium(III) Complexes Bearing Imidoylamidinate Ligands

et al. 2022

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“…Numerous natural products contain the amidino and guanidino groups [ 167 , 168 ]. Strong organic nitrogen bases are also used as ionic liquids [ 169 , 170 , 171 , 172 ], ligands in metal chelation [ 173 ], and reference bases in PA/GB measurements [ 18 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 51 , 52 , 53 , 54 , 55 , 65 , 85 , 86 , 87 ]. Figure 15 summarizes the most significant fields in which organic nitrogen superbases are found.…”

Section: Overview and Prospectsmentioning

confidence: 99%

Strong Bases and beyond: The Prominent Contribution of Neutral Push–Pull Organic Molecules towards Superbases in the Gas Phase

Raczyńska,

Gal,

Maria

2024

IJMS

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In this review, the principles of gas-phase proton basicity measurements and theoretical calculations are recalled as a reminder of how the basicity PA/GB scale, based on Brønsted–Lowry theory, was constructed in the gas-phase (PA—proton affinity and/or GB—gas-phase basicity in the enthalpy and Gibbs energy scale, respectively). The origins of exceptionally strong gas-phase basicity of some organic nitrogen bases containing N-sp3 (amines), N-sp2 (imines, amidines, guanidines, polyguanides, phosphazenes), and N-sp (nitriles) are rationalized. In particular, the role of push–pull nitrogen bases in the development of the gas-phase basicity in the superbasicity region is emphasized. Some reasons for the difficulties in measurements for poly-functional nitrogen bases are highlighted. Various structural phenomena being in relation with gas-phase acid–base equilibria that should be considered in quantum-chemical calculations of PA/GB parameters are discussed. The preparation methods for strong organic push–pull bases containing a N-sp2 site of protonation are briefly reviewed. Finally, recent trends in research on neutral organic superbases, leaning toward catalytic and other remarkable applications, are underlined.

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“…1,2 Nitrogen analogues of 1,3dicarbonyl derivatives (which are less explored than diketones) also constitute important ligands with a plethora of applications in inorganic chemistry and catalysis (Chart 1, B). 3−7 Brusso et al recently provided a comprehensive overview of the synthesis, coordination chemistry, and utilization of this widely utilized chelate ligand, 3 in which applications span from single-molecule magnets, spin crossover materials to metal− organic frameworks, and photoluminescent materials, among others. However, the exploration of β-diketiminate (or NacNac) and related chelate ligands lags behind their oxygen congeners.…”

Section: Introductionmentioning

confidence: 99%

Introducing Cationic Selenium-Containing Triazapentadiene Ligand Framework: Synthesis, Coordination Chemistry, and Antifungal Activity

Sapronov,

Khrustalev,

Chusova

et al. 2024

Inorg. Chem.

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Positively charged ligands are scarce. Here, we report the synthesis of unprecedented cationic selenium-containing triazapentadiene ligand framework. The reaction between 2pyridylselenyl reagents and NaN(CN) 2 in a 2:1 ratio produces the sodium complexes featuring the cationic selenium-containing triazapentadiene (SeTAP) ligand. The sodium-to-metal transmetalation allows facile preparation of SeTAP metal complexes, as exemplified by the reactions with CuCl 2 , AgNO 3 , NaAuCl 4 , and FeCl 3 . Density functional theory calculations have been used to analyze and characterize the chalcogen bonding interactions observed in the solid state for these compounds. Moreover, antifungal properties of the SeTAP ligand and its metal complexes were screened for in vitro activity against several phytopathogenic fungi. Phoma eupyrena exhibited prominent sensitivity against the action of most of the tested compounds.

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A chelate like no other: exploring the synthesis, coordination chemistry and applications of imidoyl amidine frameworks

Abstract: Exploration of imidoyl amidine based materials in organic and inorganic chemistry demonstrates the vast applicability of these highly versatile frameworks. The account provides a critical overview of research progress on the chemistry and complexation of these ligands.

Cited by 5 publications

References 116 publications

Photo- and Electroluminescent Neutral Iridium(III) Complexes Bearing Imidoylamidinate Ligands

Photo- and Electroluminescent Neutral Iridium(III) Complexes Bearing Imidoylamidinate Ligands

Strong Bases and beyond: The Prominent Contribution of Neutral Push–Pull Organic Molecules towards Superbases in the Gas Phase

Introducing Cationic Selenium-Containing Triazapentadiene Ligand Framework: Synthesis, Coordination Chemistry, and Antifungal Activity

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